CN109309203A - Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application - Google Patents

Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application Download PDF

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Publication number
CN109309203A
CN109309203A CN201710617358.2A CN201710617358A CN109309203A CN 109309203 A CN109309203 A CN 109309203A CN 201710617358 A CN201710617358 A CN 201710617358A CN 109309203 A CN109309203 A CN 109309203A
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China
Prior art keywords
carbon
nano
porous
composite material
lithium
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CN201710617358.2A
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Chinese (zh)
Inventor
郭峰
王亚龙
康拓
刘承浩
陈鹏
沈炎宾
卢威
陈立桅
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China Amperex Technology Ltd (tianjin)
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China Amperex Technology Ltd (tianjin)
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Priority to CN201710617358.2A priority Critical patent/CN109309203A/en
Priority to EP17919284.4A priority patent/EP3660963A4/en
Priority to KR1020197022378A priority patent/KR20190099062A/en
Priority to KR1020217020010A priority patent/KR20210084657A/en
Priority to JP2019560436A priority patent/JP2020509566A/en
Priority to PCT/CN2017/105676 priority patent/WO2019019412A1/en
Priority to US16/477,791 priority patent/US20200123008A1/en
Publication of CN109309203A publication Critical patent/CN109309203A/en
Priority to US17/733,367 priority patent/US11866332B2/en
Pending legal-status Critical Current

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Abstract

Disclose a kind of nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application.In nano carbon particle-stephanoporate framework composite material, stephanoporate framework is 1-100 microns of diameter of porous micro-sphere material, or the porous metal material of the internal void with micro-meter scale pore-size distribution, nano carbon particle are distributed in the hole of porous micro-sphere material or porous metal material and on surface.Nano carbon particle-stephanoporate framework composite material and molten metal lithium are mixed to form lithium-nano carbon particle-stephanoporate framework composite material, be present in nano carbon particle in the material can during circulating battery preferably conducting lithium ions, to inhibit the generation of metal Li dendrite, safety and the cyclical stability of battery are improved.

Description

Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their system Preparation Method and application
Technical field
The present invention relates to a kind of nanocomposite, in particular to a kind of nano carbon particle-stephanoporate framework composite material, its Lithium metal compound, their preparation method and application.
Background technique
The advantages that specific energy of lithium battery Yin Qigao, the cycle life of length, have been widely used for consumer electronics, electronic vapour The fields such as vehicle and energy storage.But at present lithium battery be compound to contain elemental lithium as positive and graphite as cathode, and The specific capacity limit of graphite negative electrodes material is about 370mAh/g, has been difficult to further increase lithium electricity based on this negative electrode material The energy density in pond, it is difficult to adapt to demand of the market to higher energy density lithium battery.Since lithium anode has high ratio Capacity (3860mAh/g), low electrode potential (- 3.04V vs standard hydrogen electrode), the specific energy of lithium battery Yin Qigao, length are followed The ring service life, high voltage and be widely used in the fields such as consumer electronics, electric car and energy storage.Lithium anode has high specific volume It measures (3860mAh/g), low electrode potential (- 3.04V vs SHE) and small density (0.59g/cm3) a series of advantages, it uses Lithium metal can significantly improve the energy density of lithium battery as battery cathode.Lithium metal can be provided as battery cathode simultaneously Lithium ion, then anode can use the higher material without elemental lithium of capacity, such as sulphur, air.
However, lithium anode battery constantly forms dendrite and " dead lithium " in cyclic process, lead to that coulombic efficiency is low, follows The ring service life is short.Importantly, the growth of dendrite is possible to that diaphragm can be pierced through and causes positive and negative anodes to connect and internal short-circuit occurs, lead Cause releases a large amount of heat, and the burning of battery is caused even to explode.The above problem makes lithium anode in the application of recent decades It is extremely limited.
Summary of the invention
The main purpose of the present invention is to provide a kind of nano carbon particle-stephanoporate framework composite material, its lithium metal are compound Object, their preparation method, electrode and electrochemical cell comprising them improve electricity to inhibit the generation of metal Li dendrite The safety in pond and/or cyclical stability.
The technical solution adopted by the present invention includes:
A kind of nano carbon particle-stephanoporate framework composite material is provided in some embodiments, wherein the porous bone Frame is 1-100 microns of diameter of porous micro-sphere material, or the internal void with micro-meter scale pore-size distribution is porous Metal material, the nano carbon particle be distributed in the hole of the porous micro-sphere material or the porous metal material and On surface.
It provides in some embodiments and a kind of prepares nano carbon particle-stephanoporate framework composite material method, comprising: It disperses carbon nanotube or carbon nano-fiber in solvent together with nano carbon particle and forms dispersion liquid, be then spray-dried；Or It is molten that micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metal material are immersed in nano carbon particle by person In liquid, then ultrasonic treatment is dried.
A kind of lithium-nano carbon particle-stephanoporate framework composite material is provided in some embodiments comprising above-mentioned Nano carbon particle-stephanoporate framework composite material, and be distributed in the nano carbon particle-stephanoporate framework composite material hole and Lithium metal on surface.
It provides in some embodiments and a kind of prepares lithium metal-nano carbon particle-stephanoporate framework composite material side Method, comprising: molten metal lithium is mixed with above-mentioned nano carbon particle-stephanoporate framework composite material, is then cooled down.
A kind of electrode is provided in some embodiments, and it includes above-mentioned lithium-nano carbon particle-stephanoporate framework composite woods Material.
A kind of electrochemical energy storage device including above-mentioned electrode is provided in some embodiments, wherein the electrochemistry Energy storage device includes electrochemical cell or supercapacitor,
At least one of the invention has the advantages that:
(1) it is porous with molten metal lithium to be mixed to form lithium-nano carbon particle-for nano carbon particle-stephanoporate framework composite material Skeletal composite, be present in nano carbon particle in the material can during circulating battery preferably conducting lithium ions, To inhibit the generation of metal Li dendrite, the safety of battery is improved.
(2) lithium-nano carbon particle-stephanoporate framework composite material may be used as the negative electrode material of battery, improve following for battery Ring stability.
(3) preparation process is simple, suitable for mass production.
(4) lithium metal-nano carbon particle-stephanoporate framework composite material can be applied to miscellaneous lithium battery, can answer For lithium metal-oxide cell, lithium metal-polymer battery, rechargeable lithium ion batteries.
Detailed description of the invention
Fig. 1 shows that the acetylene black-carbon nanotube microballoon composite material (a, b) obtained in embodiment 1 and lithium carbon micron are multiple Close the scanning electron microscope (SEM) photograph of particle (c, d).
Fig. 2 is the scanning electron microscope (SEM) photograph (amplification factor 20000) of the amplification of Fig. 1 b.
Fig. 3, which is shown, separately constitutes half-cell by the lithium carbon micron composite particles of embodiment 1, lithium piece, in 0.5mA cm-2Electricity Current density, 0.5mAh cm-2Capacity conditions under, carry out the test of half-cell cycle performance result.
Fig. 4 shows the lithium carbon micron composite particles of embodiment 1, and lithium piece separately constitutes half-cell, 0.5mA cm-2Electric current is close Degree, 0.5mAh cm-2Capacity conditions under circulation 200 circle after electrode pattern (a, b be lithium carbon micron composite particles, c, d are lithium Piece).
Fig. 5 shows that lithium carbon micron composite particles/lithium half-cell of embodiment 1 is different during constant current charge-discharge test Voltage-capacity curve when cycle-index.
Fig. 6 shows the full battery that the lithium carbon micron composite particles of embodiment 1 and lithium piece are formed with LiFePO4 respectively, Under the conditions of 1C multiplying power, the test result of the capacity retention ratio under different cycle-indexes.
Fig. 7 shows the comparison diagram for the micro-sphere material being respectively formed without nano carbon particle and when containing nano carbon particle, left Figure is the micro-sphere material that embodiment 2 obtains, and right figure is the micro-sphere material that embodiment 1 obtains.
Fig. 8 shows that the lithium carbon micron composite particles of embodiment 2, lithium piece separately constitute half-cell, in 0.5mA cm-2Electric current Density, 0.5mAh cm-2Capacity conditions under, carry out the test of half-cell cycle performance result.
Fig. 9 shows lithium-carbon fiber microballoon composite material scanning electron microscope (SEM) photo of embodiment 5.
Figure 10 shows constant current charge-discharge curve of the lithium-carbon fiber microballoon composite material of embodiment 5 as cathode.
Figure 11 shows lithium metal-nickel skeleton carbon material composition half-cell of embodiment 6, in 0.5mA cm-2Current density, 0.5mAh cm-2Capacity conditions under, the test result of half-cell cycle performance.
Figure 12 shows lithium metal-nickel skeleton carbon material of embodiment 6 and the full battery of LiFePO4 composition, in 1C multiplying power Under the conditions of, the test result of the capacity retention ratio under different cycle-indexes.
Specific embodiment
Nano carbon particle-stephanoporate framework composite material:
One aspect of the present invention provides a kind of nano carbon particle-stephanoporate framework composite material, and it includes by diameter 1-100 The porous metal material of the porous micro-sphere material of micron or the internal void with micro-meter scale pore-size distribution is constituted more Hole on framework material, and it is distributed in the nano carbon particle in the hole of stephanoporate framework material and on surface.
In some embodiments, the porous micro-sphere material include carbon nanotube or carbon nano-fiber micro-sphere material, At least one of graphite, carbonaceous mesophase spherules and porous activated carbon.
In some embodiments, the carbon nanotube or carbon nano-fiber micro-sphere material are by carbon nanotube or carbon nano-fiber It mutually entwines and reunites and formed, there are a large amount of nanoscale holes on internal and surface.Such microballoon has approximate solid Structure (similar ball of yarn structure), i.e., be full of carbon nanotube or carbon nano-fiber inside microballoon, but the carbon nanometer for reunion of entwining There are nanoscale hole between pipe or carbon nano-fiber, these holes can be used for accommodating nano carbon particle and lithium metal Grain.
In some embodiments, the carbon nanotube or carbon nano-fiber micro-sphere material are spherical or near-spherical particle, are put down Equal diameter can be 1 μm~100 μm, preferably 1 μm~25 μm；Specific surface area can be 100~1500m2/ g, preferably 150 ~500m2/g；The pore-size distribution of contained hole can be 1~200nm, preferably 1~50nm in microballoon.Containing nano carbon particle In appearance structure significant change does not occur for microballoon and microballoon without nano carbon particle, and only hole, which holds, reduces, for example, subtracting from 2.0 As low as 1.4cm3g-1。
In some embodiments, the carbon nanotube or carbon nano-fiber micro-sphere material are at least poly- with tiny spherical solid Collect any in structure, spherical aggregated structure, spherical aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure It is a kind of.
In some embodiments, the carbon nanotube includes multi-walled carbon nanotube, double-walled carbon nano-tube and single Any one in pipe or two or more combinations, the carbon nanotube optionally pass through surface-functionalized processing.It modifies and is received in carbon The group of nanotube surface may be selected from but not limited to-COOH ,-OH ,-NH2Equal groups.
In some embodiments, the graphite, carbonaceous mesophase spherules and porous activated carbon are sheet, spherical shape or near-spherical Particle shape shape, average diameter can be 50 μm~500 μm, preferably 100 μm~200 μm；Specific surface area can for 100~ 1000m2/ g, preferably 100~500m2/g；The pore-size distribution of contained hole can be 20~500nm, preferably 20~100nm.
In some embodiments, porous metal material includes Porous Cu, porous aluminum, porous zinc, porous iron, and porous nickel is more At least one of Kong Jin and porous silver.
In some embodiments, the pore-size distribution of the contained hole of porous metal material can be 100~1000 μm, preferably It is 100~500 μm；Specific surface area can be 50~500m2/ g, preferably 50~200m2/g。
In some embodiments, the nano carbon particle includes carbon black (such as Degussa carbon black), acetylene black, Ketjen black, Special close highly conductive dose of Super P, at least one of Cabot BP2000.
In some embodiments, the size of the nano carbon particle can be 1-500nm, preferably 50-200nm.
In some embodiments, in the nano carbon particle-stephanoporate framework composite material nano carbon particle relative to porous The content of skeleton can be 20~500wt%, preferably 50~200wt%.
Prepare nano carbon particle-stephanoporate framework composite material method:
One aspect of the present invention, which provides, a kind of prepares nano carbon particle-stephanoporate framework composite material method, comprising: will Carbon nanotube or carbon nano-fiber are scattered in solvent together with nano carbon particle forms dispersion liquid, is then spray-dried；Alternatively, Micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metal material are immersed in nano carbon particle solution In, then ultrasonic treatment is dried.
In some embodiments, nano carbon particle-carbon nanotube or carbon nano-fiber microballoon composite material can pass through spray The preparation of mist drying means, for example, the preparation method may include steps of:
A, carbon nano-tube/carbon nano fabric and nano carbon particle are distributed to dispersion solvent (without table by ultrasonic treatment Face activating agent) in, obtain dispersion liquid；
B, the dispersion liquid obtained in step A is sprayed by the nozzle of spray dryer, presetting inlet air temperature and outlet air Temperature, it is stirring that solution is kept in spray process；
C, cooling, i.e. acquisition nano carbon particle-carbon nano-tube/carbon nano fabric microballoon composite material.
In some embodiments, the mass ratio in step A between nano carbon particle and carbon nano-tube/carbon nano fabric can be with For 0.5:1 to 8:1, preferably 0.5:1 to 5:1, more preferable 0.5:1 to 2:1.
About " nano carbon particle " and " carbon nano-tube/carbon nano fabric ", referring to " the porous bone of nano carbon particle-above Associated description in frame composite material " part.
In some embodiments, concentration of the carbon nano-tube/carbon nano fabric in dispersion liquid can be 10~50g/L, excellent Select 10~15g/L.
In some embodiments, the solvent use can make carbon nano-tube/carbon nano fabric and nano carbon particle uniform Dispersion organic and/or inorganic liquid, for example, water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol any one or it is more The combination of kind.
In some embodiments, the solvent can be the mixture of ethyl alcohol and water that volume ratio is 1:10.
In some embodiments, it is 150~250 DEG C that the condition of spray drying, which may include: inlet air temperature, and leaving air temp is 75 DEG C or more, such as 75~150 DEG C, or be 90 DEG C or more；One preferred spray drying condition includes: that inlet air temperature is 190 ~210 DEG C, leaving air temp is 90~110 DEG C.
In some embodiments, spray velocity when spray drying can be 1 ml/min to 100 liters/min.
In some embodiments, using micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metals Material prepares nano carbon particle-stephanoporate framework composite material as stephanoporate framework material, using dipping ultrasonic method.The dipping Ultrasonic method may include: to impregnate micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metal material In nano carbon particle solution, then ultrasonic treatment is dried.
In some embodiments, the nano carbon particle solution includes the aqueous solution of nano carbon particle, or molten in ethyl alcohol Agent or the solution in ethyl alcohol and water mixed solvent.
In some embodiments, concentration of the nano carbon particle in nano carbon particle solution can be 5~50g/L, preferably 10~30g/L.
Lithium metal-nano carbon particle-stephanoporate framework composite material
One aspect of the present invention provides a kind of lithium metal-nano carbon particle-stephanoporate framework composite material, and it includes above-mentioned Nano carbon particle-stephanoporate framework composite material, and be distributed in the nano carbon particle-stephanoporate framework composite material hole And the lithium metal on surface, wherein nano carbon particle-stephanoporate framework composite material as skeleton adulteration lithium metal, lithium metal with Simple substance form is present in its hole or (based on pore interior, the lithium metal on surface is less) on its surface.
In some embodiments, the quality of lithium metal be the composite material gross mass 1%~95%, preferably 10%~ 70%, more preferable 20%~70%.
Prepare lithium metal-nano carbon particle-stephanoporate framework composite material method
One aspect of the present invention provide it is a kind of prepare lithium metal-nano carbon particle-stephanoporate framework composite material method, Include: to mix molten metal lithium with above-mentioned nano carbon particle-stephanoporate framework composite material, then cools down.
In some embodiments, molten metal lithium and the mixing of nano carbon particle-porous microballoon composite material can To include being stirred lithium metal and porous micro-sphere material under heating.
In some embodiments, described be stirred may include pre- whipping step and quick whipping step, wherein stirring in advance It includes in relatively low temperature (for example, about 200 DEG C -230 DEG C) that lithium metal and nano carbon particle-stephanoporate framework is multiple for mixing step The mixture of condensation material stirs at low speed (for example, about 50 revs/min -100 revs/min) short period (such as 1-5 minutes), quickly Whipping step include relatively high temperature (for example, about 230 DEG C -300 DEG C) quickly stirring (for example, about 150 revs/min - 1000 revs/min, preferably 200 revs/min -800 revs/min).
About " porous micro-sphere material ", referring to the correlation in " nano carbon particle-stephanoporate framework composite material " part Description.
In some embodiments, molten metal lithium can wrap with the mixing of nano carbon particle-porous metal composite material Include step nano carbon particle-porous metal composite material immersed in molten metal lithium.
In some embodiments, the quality of lithium metal be the composite material gross mass 1%~95%, preferably 10%~ 70%, more preferable 20%~70%.
Lithium metal-nano carbon particle-stephanoporate framework composite material purposes
One aspect of the present invention provides a kind of electrode, compound comprising above-mentioned lithium metal-nano carbon particle-stephanoporate framework Material is as electrode material.
In some embodiments, lithium metal-nano carbon particle-stephanoporate framework composite material may be used as the work of battery cathode Property material or be directly used as electrode (using porous metals skeleton).
One aspect of the present invention provides a kind of electrochemical energy storage device comprising above-mentioned electrode.
In some embodiments, electrochemical energy storage device is electrochemical cell, and the electrode is used as battery cathode.
In some embodiments, electrochemical cell includes lithium battery, lithium metal-oxide cell, the secondary electricity of lithium metal-sulphur Pond or metal lithium-air battery.
In some embodiments, electrochemical energy storage device is supercapacitor, and the electrode is used as the one of supercapacitor A electrode slice.
Lithium-nano carbon particle-stephanoporate framework composite material provided by the invention exists when being applied to electrochemical cell Nano carbon particle in the material can during circulating battery preferably conducting lithium ions, to inhibit metal Li dendrite Generation, to improve the safety of battery, and can also be improved the cyclical stability of battery.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of nano carbon particle-stephanoporate framework composite material, wherein the stephanoporate framework is diameter 1-100 microns of porous micro-sphere material, or the porous metal material of the internal void with micro-meter scale pore-size distribution, The nano carbon particle is distributed in the hole of the porous micro-sphere material or the porous metal material and on surface.
Specific embodiment 2 is the nano carbon particle according to specific embodiment 1-stephanoporate framework composite material, Described in porous micro-sphere material include carbon nanotube or carbon nano-fiber micro-sphere material, graphite, carbonaceous mesophase spherules and more At least one of mesoporous activated carbon, wherein the carbon nanotube or carbon nano-fiber micro-sphere material are by carbon nanotube or carbon Nanowire Dimension is mutually entwined reunion and is formed, is full of carbon nanotube or carbon nano-fiber inside microballoon, with largely receiving on internal and surface Metrical scale hole；
And/or the porous metal material includes Porous Cu, porous aluminum, porous zinc, porous iron, porous nickel, porous gold and At least one of porous silver,
And/or the nano carbon particle includes carbon black, acetylene black, Ketjen black, special close highly conductive dose of Super P, Cabot At least one of BP2000.
Specific embodiment 3 is the nano carbon particle according to specific embodiment 1 or 2-stephanoporate framework composite material, Wherein the size of nano carbon particle can be 1-500nm, preferably 50-200 nanometers.
Specific embodiment 4 is that nano carbon particle-stephanoporate framework according to any one of specific embodiment 1-3 is multiple Condensation material, wherein the nano carbon particle is 20-500wt% relative to the bone porous content.
Specific embodiment 5 is that nano carbon particle-stephanoporate framework according to any one of specific embodiment 2-4 is multiple Condensation material, wherein the carbon nanotube or the specific surface area of carbon nano-fiber micro-sphere material are 100~1500m2/g；
And/or the aperture of hole contained by the carbon nanotube or carbon nano-fiber micro-sphere material is 1~200nm；
And/or the carbon nanotube or carbon nano-fiber micro-sphere material at least have tiny spherical solid aggregated structure, ball Any one in shape aggregated structure, spherical aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure；
And/or the carbon nanotube includes any in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube A combination of one or more, the carbon nanotube optionally pass through surface-functionalized processing.
Specific embodiment 6 is a kind of to prepare the porous bone of nano carbon particle-described in any one of specific embodiment 1-5 The method of frame composite material, comprising:
It disperses carbon nanotube or carbon nano-fiber in solvent together with nano carbon particle and forms dispersion liquid, it is then spraying It is dry；
It is received alternatively, micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metal material are immersed in In rice carbon particle solution, then ultrasonic treatment is dried.
Specific embodiment 7 is the method according to specific embodiment 6, wherein by carbon nanotube or carbon nano-fiber The method being spray-dried together with nano carbon particle includes the following steps:
A, carbon nano-tube/carbon nano fabric and nano carbon particle are distributed to dispersion solvent (without table by ultrasonic treatment Face activating agent) in, obtain dispersion liquid；
B, the dispersion liquid obtained in step A is sprayed by the nozzle of spray dryer, presetting inlet air temperature and outlet air Temperature, it is stirring that solution is kept in spray process；
C, cooling, i.e. acquisition nano carbon particle-carbon nano-tube/carbon nano fabric microballoon composite material.
Specific embodiment 8 is the method according to specific embodiment 7, wherein nano carbon particle and carbon in step A Mass ratio 0.5:1 to 8:1 between nanotube/carbon nano-fiber；
And/or concentration of the carbon nano-tube/carbon nano fabric in dispersion liquid is 10~50g/L；
And/or dispersion solvent includes any one or more of water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol Combination.
Specific embodiment 9 is the method according to specific embodiment 7 or 8, and wherein inlet air temperature is 190~210 DEG C, leaving air temp is 90~110 DEG C,
And/or spray velocity is 1 ml/min to 100 liters/min.
Specific embodiment 8 is the method according to specific embodiment 6, wherein the nano carbon particle solution includes Nano carbon particle aqueous solution；
And/or concentration of the nano carbon particle in nano carbon particle solution is 5~50g/L.
Specific embodiment 10 is a kind of lithium metal-nano carbon particle-stephanoporate framework composite material, including specific reality Nano carbon particle described in any one of mode 1-5-stephanoporate framework composite material is applied, and to be distributed in the nano carbon particle-more Lithium metal in the hole of hole on framework composite material and on surface.
Specific embodiment 11 is lithium-nano carbon particle-stephanoporate framework composite wood according to specific embodiment 10 Material, wherein the quality of lithium metal is the lithium-nano carbon particle-stephanoporate framework composite material total quality 1%~95%.
Specific embodiment 12 be it is a kind of prepare lithium metal-nano carbon particle-stephanoporate framework composite material method, packet It includes: nano carbon particle described in any one of molten metal lithium and specific embodiment 1-5-stephanoporate framework composite material is mixed It closes, then cools down.
Specific embodiment 13 is the method according to specific embodiment 11, wherein molten metal lithium and nano-sized carbon The mixing of particle-porous microballoon composite material includes:
Lithium metal and porous micro-sphere material are stirred under heating；
Or nano carbon particle-porous metal composite material is immersed in molten metal lithium.
Specific embodiment 14 is the method according to specific embodiment 13, wherein being stirred including stirring step in advance Rapid and quick whipping step, wherein pre- whipping step is included in 200 DEG C -230 DEG C for lithium metal and nano carbon particle-stephanoporate framework The mixture of composite material with 50 revs/min -100 revs/min of stirrings 1-5 minutes, quick whipping step is included in 230 DEG C -300 It DEG C is quickly stirred with 150 revs/min -1000 revs/min.
Specific embodiment 15 is a kind of electrode, and it includes lithium-nano carbon particles-described in specific embodiment 10 or 11 Stephanoporate framework composite material.
Specific embodiment 16 is a kind of electrochemical energy storage device, including electrode described in specific embodiment 15； The electrochemical energy storage device includes electrochemical cell or supercapacitor.
Specific embodiment 17 is according to the electrochemical energy storage device of specific embodiment 16, and wherein electrochemical cell includes Lithium battery, lithium metal-oxide cell, lithium metal-sulfur rechargeable battery or metal lithium-air battery.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
Postscript, used various products structural parameters, various reaction partners and technique item among following examples Part is more typical example, but is verified by inventor's a large number of experiments, in the other different structures of those listed above Parameter, other types of reaction partner and other process conditions are also applicable, and also equal attainable cost invention is claimed Technical effect.
Embodiment 1
First by 2g outer diameter be 20-30nm multi-walled carbon nanotube (Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) and 200mL deionized water is added in 2g acetylene black (Alfa Aesar company), rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W are super Sonic probe is ultrasonically treated 5 hours, keeps sample evenly dispersed.After spray dryer is added in sample.Inlet air temperature is set as 200 DEG C, leaving air temp is set in 150 DEG C, and atomisation pressure is set as 40MPa, and sample volume is set as 500mL/h, after drying to obtain the final product To acetylene black-carbon nanotube microballoon composite material.Nitrogen adsorption desorption test is carried out to the composite material, microballoon specific surface area is 103m2/ g, average pore size 15.2nm.
100mg Battery grade lithium metal and the above-mentioned acetylene black of 100mg-carbon nanotube microballoon composite material are weighed, is placed in gold Belong in the inert heater of lithium, be heated to 200 degrees Celsius with 50 revs/min after pre- stirring 2 minutes under 230 degrees celsius with 200 revs/min are stirred 20 minutes, and mixing terminates, and is cooled to room temperature, and whole process carries out in the glove box that argon gas is protected, water Content is divided to be lower than 10ppm, oxygen content is lower than 10ppm.Obtain the compound micron particles of lithium-carbon.It is tested by weighing, lithium is in lithium carbon Mass percent in micron composite particles is 67.3%.
Fig. 1 shows that the acetylene black-carbon nanotube microballoon composite material (a, b) obtained in embodiment 1 and lithium carbon micron are multiple Close the scanning electron microscope (SEM) photograph of particle (c, d).
Fig. 2 is the scanning electron microscope (SEM) photograph (amplification factor 20000) of the amplification of Fig. 1 b, and the particulate material in circle is carbon Nano particle (acetylene black nano particle).
It takes the lithium carbon micron composite particles of above-mentioned acquisition, lithium piece to separately constitute half-cell and (takes the lithium carbon micron of above-mentioned acquisition It is 1.5cm that 20~40mg of composite particles, which is pressed in diameter, with a thickness of on the foam copper of 1mm, using the material as cathode；It will be with a thickness of 400 μm, the lithium piece that diameter is 1.5cm is as anode；2025 buttons are formed using Celgard diaphragm and above-mentioned positive and negative electrode material Battery), in 0.5mA cm-2Current density, 0.5mAh cm-2Capacity conditions under, carry out the test of half-cell cycle performance.Fig. 3 Show half-cell cycle performance test result, cyclic curve when left figure is using lithium carbon micron composite particles, right figure is lithium Piece cyclic curve.It can be seen from the figure that lithium carbon micron composite particles are just shown very in the incipient stage compared with metal lithium sheet Small polarizing voltage shows specific surface area big possessed by the material, and recycles later period polarizing voltage there is no big variation, Demonstrate material structure and surface solid electrolyte interface (SEI) layer in cyclic process) stabilization.
Fig. 4 shows lithium carbon micron composite particles, and lithium piece separately constitutes half-cell, 0.5mA cm-2Current density, 0.5mAh cm-2Capacity conditions under electrode pattern (a, b are lithium carbon micron composite particles, c, d are lithium piece) after 200 circle of circulation.For lithium piece, Sample surfaces have been covered with dendrite after circulation, this brings great security risk to battery.Lithium carbon micro-composites are reviewed, Sample still keeps grain structure after circulation, again demonstrates the stability of the material structure in cyclic process.
Fig. 5 shows lithium carbon micron composite particles/lithium half-cell different cycle-indexes during constant current charge-discharge test When voltage-capacity curve (size of current 0.74mA/cm-2).Lithium carbon micron is compound after 500 circle of circulation under the conditions of 1C multiplying power The capacity of particle is basically unchanged, show material circulation when surface SEI layers it is more stable, lithium metal will not be consumed always.
The full battery of lithium carbon micron composite particles and lithium piece respectively with LiFePO4 composition is taken (to take lithium carbon micron composite particles It is 1.5cm that 20~40mg, which is pressed in diameter, with a thickness of on the foam copper of 1mm, using the material as cathode；LiFePO4 (LFP) electricity Pole pole piece (Suzhou take in the fresh New Energy Technology Co., Ltd. production.Surface density is 0.7mAh/cm2) as anode 2025 buttons of composition Battery), under the conditions of 1C multiplying power (positive and negative electrode capacity is respectively 1.4mAh and 40mAh), measure the capacity under different cycle-indexes Conservation rate.Fig. 6 shows test result.As shown in fig. 6, under the conditions of 1C multiplying power after 600 circle of circulation, lithium carbon micron composite particles Discharge capacitance with the full battery of LiFePO4 composition is 92.8%, and using lithium piece as the full battery of cathode, capacity one Straight decline, almost without capacity after recycling 150 times.
Embodiment 2
Other than without using acetylene black, carbon nanotube micro-sphere material is prepared in the same manner as in Example 1.The microballoon material The specific surface area of material is 151m2/ g, average pore size 18.7nm.Fig. 7 is shown without nano carbon particle (left figure) and containing nanometer The comparison diagram for the micro-sphere material being respectively formed when carbon particle (right figure).It can be seen that micro-sphere material after carbon nano-particle is added Appearance structure significant change does not occur.
Using above-mentioned carbon nanotube micro-sphere material, lithium carbon micron composite particles, lithium are prepared in the same manner as in Example 1 Mass percent in lithium carbon micron composite particles is 40.4%.
The lithium carbon micron composite particles of above-mentioned acquisition, lithium piece are taken to separately constitute half-cell, in 0.5mA cm-2Current density, 0.5mAh cm-2Capacity conditions under, carry out the test of half-cell cycle performance.Fig. 8 shows half-cell cycle performance test knot Fruit.As shown in figure 8, the lithium carbon micron composite particles using embodiment 2 form half-cell, with the increase of cycle-index, sample Polarizing voltage persistently increase, show that SEI layers of sample surfaces gradually thicken, this is because lithium metal is led with electrolyte sustained response It causes.
Embodiment 3
Nano carbon particle-stephanoporate framework composite material and compound of lithium carbon micron are prepared in the same manner as in Example 1 Grain, only replaces the acetylene black in embodiment 1 with Ketjen black (Ketjen black ECP 600JD).Lithium is compound in lithium carbon micron Mass percent in particle is 60.0%.The pattern and the performance test results of resulting materials are similar to Example 1.
Embodiment 4
Nano carbon particle-stephanoporate framework composite material and compound of lithium carbon micron are prepared in the same manner as in Example 1 Grain, only replaces the acetylene black in embodiment 1 with Degussa carbon black (Printex XE-2).Lithium is in lithium carbon micron composite particles Mass percent be 51.8%.The pattern and the performance test results of resulting materials are similar to Example 1.
Embodiment 5
200mL is added in 2g carbon nano-fiber (Alfa Aesar company) and 2g acetylene black (Alfa Aesar company) first Deionized water, it is rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W ultrasonic probe are ultrasonically treated 5 hours, divide sample uniformly It dissipates.After spray dryer is added in sample.Inlet air temperature is set as 200 DEG C, and leaving air temp is set in 150 DEG C, spraying pressure Power is set as 40MPa, and sample volume is set as 500mL/h, obtains acetylene black-carbon nano-fiber microballoon composite material after dry, Pattern is similar with the acetylene black in embodiment 1-carbon nanotube microballoon composite material.Nitrogen adsorption desorption is carried out to the composite material Test, microballoon specific surface area are 98m2/ g, average pore size 13.1nm.
100mg Battery grade lithium metal and the above-mentioned acetylene black of 100mg-carbon nano-fiber microballoon composite material are weighed, is placed in pair In the inert heater of lithium metal, be heated to 200 degrees Celsius with 50 revs/min after pre- stirring 2 minutes under 230 degrees celsius It is stirred 20 minutes with 200 revs/min, mixing terminates, and is cooled to room temperature, and whole process carries out in the glove box that argon gas is protected, Moisture content is lower than 10ppm, and oxygen content is lower than 10ppm.Obtain the compound micron particles of lithium-carbon.It is tested by weighing, lithium is in lithium Mass percent in carbon micron composite particles is 36.3%.Fig. 9 shows the scanning of the lithium-carbon fiber microballoon composite material Electron microscope (SEM) photo, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 25000 times.
Figure 10 shows constant current charge-discharge curve of the lithium-carbon fiber microballoon composite material as cathode.It can from the figure Out, lithium-carbon fiber microballoon composite material polarizing voltage very little when starting shows that material has big specific surface area, can be greatly Ground reduces current density, effectively inhibits the generation of lithium Zhi Jing.It avoids due to dendrite short circuit bring cell safety hidden danger, thus more It is possible that being applied in actual high energy density cells system.
Embodiment 6
It is 1.5cm by 2g diameter, with a thickness of 500-1000 μm of porous-metal nickel (pore-size distribution is at 100-500 μm) skeleton Material is placed in 100mL, and concentration is then to surpass the solution in acetylene black (Alfa Aesar company) aqueous solution of 20g/L Sound decentralized processing 1h.By obtained mixture, standing and drying obtains including the porous of nano carbon particle afterwards for 24 hours in 80 DEG C of baking ovens Metallic nickel framework material.By comprising nano-scale carbon particle porous-metal nickel framework material immerse molten metal lithium in get To lithium metal-nickel skeleton material.It is tested by weighing, mass percent of the lithium in lithium metal-nickel skeleton material is 50.0% [(lithium metal-nickel skeleton material quality-metal nickel skeleton quality)/lithium metal-nickel skeleton material quality].
The lithium metal-nickel skeleton carbon material is formed into half-cell, 0.5mA cm-2Current density, 0.5mAh cm-2Capacity Under the conditions of, half-cell cycle performance is tested, as a result as shown in figure 11.It can be seen from figure 11 that cycles samples 200 enclose after-polarization electricity Pressure is basically unchanged, and being slightly increased is caused by gradually being thickend as surface SEI layers；And capacity and coulomb under full battery test condition The stabilization of efficiency further demonstrates that the stabilization of material structure and surface SEI layers.In addition, by lithium metal-nickel skeleton carbon material and phosphorus The full battery of sour iron lithium composition measures the capacity retention ratio under different cycle-indexes under the conditions of 1C multiplying power, as a result such as Figure 12 institute Show.
It should be appreciated that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all at this Made any modifications, equivalent replacements, and improvements etc., should be included in protection model of the invention within the spirit and principle of invention Within enclosing.

Claims (10)

1. a kind of nano carbon particle-stephanoporate framework composite material, it is characterised in that the stephanoporate framework is 1-100 microns of diameter Porous micro-sphere material, or the porous metal material of the internal void with micro-meter scale pore-size distribution, the nano-sized carbon Distribution of particles is in the hole of the porous micro-sphere material or the porous metal material and on surface.
2. nano carbon particle according to claim 1-stephanoporate framework composite material, it is characterised in that the porous is micro- Ball material include in carbon nanotube or carbon nano-fiber micro-sphere material, graphite, carbonaceous mesophase spherules and porous activated carbon at least One kind, wherein the carbon nanotube or carbon nano-fiber micro-sphere material reunion mutually entwined by carbon nanotube or carbon nano-fiber and It is formed, carbon nanotube or carbon nano-fiber is full of inside microballoon, there are a large amount of nanoscale holes on internal and surface；
And/or the porous metal material includes Porous Cu, porous aluminum, porous zinc, porous iron, porous nickel, porous gold and porous At least one of silver,
And/or the nano carbon particle includes carbon black, acetylene black, Ketjen black, special close highly conductive dose of Super P, Cabot At least one of BP2000.
3. nano carbon particle according to claim 1-stephanoporate framework composite material, it is characterised in that the nano carbon particle It is 20-500wt% relative to the bone porous content.
4. nano carbon particle according to claim 2-stephanoporate framework composite material, it is characterised in that the carbon nanotube or The specific surface area of carbon nano-fiber micro-sphere material is 100-1500m2/g；
And/or the aperture of hole contained by the carbon nanotube or carbon nano-fiber micro-sphere material is 1-200nm；
And/or the carbon nanotube or carbon nano-fiber micro-sphere material at least have tiny spherical solid aggregated structure, spherical shape poly- Collect any one in structure, spherical aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure；
And/or the carbon nanotube includes any one in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube Or two or more combinations, the carbon nanotube optionally pass through surface-functionalized processing.
5. a kind of prepare nano carbon particle of any of claims 1-4-stephanoporate framework composite material method, spy Sign be the described method includes:
It disperses carbon nanotube or carbon nano-fiber in solvent together with nano carbon particle and forms dispersion liquid, then do by spraying It is dry；
Alternatively, micrometer level porous graphite, carbonaceous mesophase spherules, porous activated carbon or porous metal material are immersed in nano-sized carbon In particle solution, then ultrasonic treatment is dried.
6. a kind of lithium metal-nano carbon particle-stephanoporate framework composite material, it is characterised in that including any in claim 1-4 Nano carbon particle-stephanoporate framework composite material described in, and it is distributed in the nano carbon particle-stephanoporate framework composite material Lithium metal in hole and on surface.
7. lithium metal-nano carbon particle-stephanoporate framework composite material according to claim 6, it is characterised in that lithium metal Quality be the composite material gross mass 1%~95%.
8. a kind of prepare lithium metal-nano carbon particle-stephanoporate framework composite material method, it is characterised in that the method packet It includes: molten metal lithium is mixed with nano carbon particle of any of claims 1-4-stephanoporate framework composite material, Then it cools down.
9. a kind of electrode, it is characterised in that compound comprising lithium metal-nano carbon particle-stephanoporate framework described in claim 6 or 7 Material.
10. a kind of electrochemical energy storage device, it is characterised in that including electrode as claimed in claim 9, the electrochemical energy storage dress It sets including electrochemical cell or supercapacitor.
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Application publication date: 20190205